Method of producing diol by hydrogenolysis of peroxide polymers with reactivation of Raney nickel catalyst

ABSTRACT

A poisoned Raney nickel catalyst from the hydrogenolysis of an organic peroxide polymer is reactivated by treating the catalyst with a 0.1-5 N solution of an activating reagent selected from the group consisting of ammonia, and an alkali metal or an alkaline earth metal hydroxide, carbonate or carboxylate having 1-4 carbon atoms at 20 DEG -200 DEG C under an inert gas atmosphere.

This is a division of application Ser. No. 427,683, filed Dec. 26, 1973,now U.S. Pat. No. 3,896,051.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for reactivating poisonedRaney nickel which has been used for the hydrogenolysis of organicperoxide polymers.

2. Description of the Prior Art

Methods are known for the reactivation of poisoned Raney nickelcatalysts. However, no techniques are known for the reactivation ofpoisoned Raney nickel catalysts which have been used for thehydrogenolysis of organic peroxide polymers. When Raney nickel catalystsare used for the hydrogenolysis of organic peroxide polymers, thecatalysts are inactivated by certain catalyst poisons.

A need, therefore, exists for a technique for reactivating Raney nickelcatalysts which have been specifically deactivated in the hydrogenolysisreaction of organic peroxide polymers.

SUMMARY OF THE INVENTION

Accordingly, one object of the present invention is to provide a methodfor reactivating poisoned Raney nickel catalysts.

Briefly, this object and other objects of the invention as hereinafterwill become more readily apparent can be attained by providing a methodfor the reactivation of a poisoned Raney nickel catalyst used for thehydrogenolysis of an organic peroxide polymer by treating the catalystwith a 0.1 - 5 N solution of an activating reagent selected from thegroup consisting of ammonia, an alkali metal or an alkaline earth metalhydroxide, carbonate or carboxylate having 1-4 carbon atoms at 20°-200°Cunder an inert gas atmosphere.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The poisoned Raney nickel catalysts to which the process of the presentinvention is applicable include Raney nickel catalyst which are modifiedby small amounts of copper, chromium, iron, or the like which are usedin the hydrogenolysis of organic peroxide polymers. The organic peroxidepolymers which are subjected to hydrogenolysis include peroxide polymersof olefins which include conjugated diolefins such as butadiene,isoprene, 2-ethyl - 1,3-butadiene, 2,3-dimethyl-1,3-butadiene,2,5-dimethyl-2,4-hexadiene, alkyl substituted conjugated diolefinsthereof: cyclo substituted conjugated diolefins such as cyclopentadiene,cyclohexadiene, dimethylfuran, furan: alkyl substituted cyclo conjugateddiolefins, and indene and styrene.

It has been found that organic peroxide polymers can be subjected tohydrogenolysis in the presence of a Raney nickel catalyst. However theorganic peroxide polymers easily poison the Raney nickel catalystsbecause of certain inherent chemical properties. If prior tohydrogenolysis the Raney nickel catalyst is contacted with the organicperoxide polymer, the degree of poisoning is substantial which resultsin low yields of the diol product and the reaction rate is low.

The degree of catalyst poisoning however, can be significantly reducedby improving the contact between the organic peroxide polymer and thecatalyst in the hydrogenation reaction. In order to improve the contactbetween the catalyst and the polymer, the catalyst is suspended in amedium and then exposed to a hydrogen atmosphere whereby the hydrogen isabsorbed. At the same time the organic peroxide polymer is added to themedium which of course dilutes it, through a high pressure, small amountconstant volume pump, at a rate the same or less than the rate ofhydrogenolysis of the polymer. In the hydrogenolysis reaction, however,poisoning materials such as organic acids, polymers, and the likecontinue to be absorbed on the surface of the catalyst which in turndecreases the amount of active surface area of the catalyst and resultsin a rapid decrease in activity even though the contact method improvesthe reaction. Thus, the amount of the organic peroxide polymer which canbe hydrogenated per unit amount of the Raney nickel catalyst is limitedand of course, it is consumed as the reaction proceeds.

An investigation into the problem of the deactivation of the catalysthas revealed that Raney nickel catalysts poisoned by organic peroxidepolymers can be reactivated by treating the inactivated catalyst with asolution of an activating reagent such as ammonia, an alkali metal or analkaline earth metal hydroxide, carbonate or carboxylate having 1-4carbon atoms under an inert gas atmosphere after each hydrogenolysisreaction. This method of reactivation of a poisoned Raney nickelcatalyst which is presently used in the hydrogenolysis of organicperoxide polymers has heretofore been unknown. When the procedure isrepeatedly used to remove the poison from the catalyst, the catalyst canbe reused from 50 to 100 times.

In the reactivation of Raney nickel, the temperature at which thecatalyst is treated, the concentration of the activating reagent and thetreatment time all influence the degree of activation. The treatmenttemperature usually ranges from 20° to 200°C, preferably 50° to 120°C,expecially 70° to 120°C. If the treatment temperature is greater than200°C the aluminum component of the Raney nickel catalyst is dissolvedand consequently the nickel atoms are rearranged. Also, the crystallineparticles are increased and the catalytic activity is decreased. Fromthe viewpoint of catalyst life, it is preferably that the temperature belower. However, at temperatures less than 20°C, the separation of theabsorbed poison from the Raney nickel catalyst is too slow and thetreatment time is too long. Suitable media for the activating reagentsinclude water, and lower alcohols such as methanol, ethanol andisopropanol. Satisfactory treatment results are also achieved when theconcentration of the activating reagent ranges from 0.1 to 5 N.

The treatment time depends upon the concentration of the activatingreagent, the treatment temperature and the ratio of the organic peroxidepolymer to the Raney nickel catalyst in the hydrogenolysis reaction andis usually 2 to 8 hours. The treatment conditions for the Raney nickelcatalyst depend upon the ratio of the organic peroxide polymer to theRaney nickel, which must be severe at increased ratios. From theviewpoint of catalyst life, severe treatment times are preferably usedrather than using increased treatment temperatures. Suitable inert gaseswhich can be used in the treatment of the poisoned Raney nickel catalystinclude hydrogen, nitrogen and the like. These gases do not adverselyeffect the activity of the catalyst, and preferably hydrogen is used.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples which are providedherein for purposes of illustration only and are not intended to belimiting unless otherwise specified.

EXAMPLE 1

Into a 200 cc autoclave equipped with an electromagnetic stirrer, 10 gof Raney nickel (manufactured by Kawaken Fine Chemical K.K.) and 50 g oftetrahydrofuran were charged. Further, a 60 g solution of 20 g isopreneperoxide polymer in tetrahydrofuran was charged to the autoclave at 60°Cunder a hydrogen pressure of 50 kg/cm² over 2 hours by a small, constantamount injection pump. After the hydrogenolysis was completed thecatalyst was separated, and the reaction mixture was analyzed by gaschromatography. The reaction mixture contained 1.6 g of2-methyl-1,2-butanediol, 1.5 g of 2-methyl-3,4 butanediol and 6.4 g of2-methyl-1,4-butanediol.

The total yield of the diols based on the isoprene peroxide polymer was45.7%. The poisoned Raney nickel catalyst and 100 cc of an aqueous 0.5N--NaOH solution were charged into the 200 cc autoclave equipped with anelectromagnetic stirrer, and the mixture was heated and stirred at 90°Cfor 3 hours under a hydrogen atmosphere to activate the catalyst. Thecatalyst was separated, and thereafter was used for the hydrogenolysisof the isoprene peroxide polymer. The operation was repeated 30 timeswith the same catalyst, and no decrease in activity of the catalyst wasnot found.

EXAMPLES 2 - 10

In the autoclave of Example 1, each of the peroxide polymers shown inTable 1 were hydrogenated under the reaction conditions shown inTable 1. After each hydrogenolysis reaction, the poisoned Raney nickelcatalyst was treated under the conditions shown in Table 1. This cyclewas repeated a number of times as shown in each Example in the table.The results are shown in Table 1.

                                      Table 1                                     __________________________________________________________________________    Reaction Conditions                                                                                Reac-                                                                         tion                                                                              Reac-                                                                              Repeated                                                                           Reactivation Conditions                                     Raney                                                                             tempe-                                                                            tion use of         Tempe-                           Exam-                                                                             Peroxide Polymer                                                                           nickel                                                                            rature                                                                            pressure                                                                           catalyst       rature                           ple  (g)   (mole)                                                                              (g) (°C)                                                                       (kg/cm.sup.2)                                                                      (time)                                                                             Alkali    (°C)                      __________________________________________________________________________        isoprene peroxide                                                             polymer      10  60  50   1                                               2    20    0.20                                                                      "                           0.5N-Na.sub.2 CO.sub.3                          20   0.20   10  60  50   40   100 cc    90                                   2,5-dimethyl-2,4-                                                             hexadiene peroxide                                                            polymer                                                                   3    20   0.14   10  50  70   1                                                      "                           3N-ammonia                                      20    0.14  10  50  70   22   100 cc    100                                  2,5-dimethyl-2,4-                                                             hexadiene peroxide                                                            polymer      10  50  50   1                                               4*   20    0.14                                                                      "                           0.1N-KOH aq.sol.                                20     0.14 10  50  50   35   100 cc    90                                   2,5-dimethyl-2,4-                                                             hexadiene peroxide                                                            polymer                                                                   5*   20    0.14  7   50  70   1                                                      "                           0.5N-NaOH aq.                                   20    0.14  7   50  70   45   sol. 100 cc.                                                                            90                                   2-ethyl-1,3-butadiene                                                         peroxide polymer                                                                           10  60  50   1                                               6    20    0.18                                                                      "                           0.5N-Ba(OH).sub.2                               20    0.18  10  60  50   25   aq. sol. 100 cc                                                                         100                                  2,3-dimethyl-1,3-                                                             butadiene peroxide                                                                         10  60  80   1                                                   polymer                                                                   7    20    0.18                                                                      "                           0.2N-LiOH                                       20    0.18  10  60  80   15   aq. sol. 100 cc                                                                         120                                  cyclopentadiene                                                               peroxide polymer                                                                           10  50  70   1                                               8    20    0.20                                                                      "                           4N-NaOH aq. sol.                                20    0.20  10  50  70   40   100 cc    70                                   styrene peroxide                                                              polymer      10  40  20   1                                               9    20    0.14                                                                      "                           0.5N-KOH ethanol                                20   0.14   10  40  20   10   sol. 100 cc                                                                             90                                   styrene peroxide                                                              polymer      10  40  20   1                                               10   20   0.14                                                                       "                           1N-AoONa sol.                                   20    0.14  10  40  20   50   100 cc    90                                   Product                                                                                                             Total                                                                         yield                               Exam-                                     diol                                ple Diol (g)                              (%)                                 __________________________________________________________________________        2-methyl-1,2-     2-methyl-3,4-                                                                          2-methyl-1,4-                                      butanediol        butanediol                                                                             butanediol 45.7                                2   1.7               1.5      6.3                                                "                 "        "                                                  1.4               1.3      6.0        41.9                                3   2,5-dimethyl-2,5-hexanediol                                                                              17.1       83.2                                    "                          16.7       81.2                                4*  2,5-dimethyl-2,5-hexanediol                                                                              17.0       82.7                                    "                          16.5       80.3                                5*  2,5-dimethyl-2,5-hexanediol                                                                              17.1       83.2                                    "                          16.8       81.8                                    2-ethyl-1,2-      2-ethyl-3,4-                                                                           2-ethyl-1,4-                                       butanediol        butanediol                                                                             butanediol 72.9                                6   1.9               1.1      5.8                                                "                 "        "                                                  1.7               1.0      5.5        69.5                                    2,3-dimethyl-1,2- 2,3-dimethyl-1,4-                                           butanediol        butanediol          86.4                                7   3.7               6.5                                                         "                 "                   84.7                                    3.6               6.4                                                     8   1,4-cyclopentanediol                                                                            15.5                74.                                     "                 15.1                72.                                 9   benzyl alcohol 1.3                                                                              phenylglycol 16.3   88.                                     benzyl alcohol 1.2                                                                              phenylglycol 15.7   85.                                 10  benzyl alcohol 1.3                                                                              phenylglycol 16.2   88.                                     benzyl alcohol 1.2                                                                              phenylglycol 15.7   85.                                 __________________________________________________________________________     *In Example 4, a modified Raney nickel catalyst containing 1% chromium wa     used.                                                                         *In Example 5, the treatment time was 5 hours while in the other Examples     the treatment time was 3 hours.                                          

EXAMPLE 11

Into a 200 cc autoclave equipped with an electromagnetic stirrer, 10 gof Raney nickel (manufactured by Kawaken Fine Chemical K.K.) and 50 g ofethyl acetate were charged. Further, a 60 g solution of 0.23 molebutadiene peroxide polymer (as C₄ H₆ O₂) in ethyl acetate was chargeinto the autoclave at 70°C under a hydrogen pressure of 50 kg/cm² over 2hours by a small, constant amount injection pump. After thehydrogenolysis was completed, the catalyst was separated and thereaction mixture was analyzed by gas chromatography.

The reaction mixture contained 11.6 g of 1,4-butanediol, 3.82 g of1,2-butanediol and 1.95 g of other diols.

The yield of 1,4-butanediol based on the butadiene peroxide polymer was56%. The poisoned Raney nickel catalyst and 100 cc of an aqueous 0.5N--NaOH solution were charged into the 200 cc autoclave equipped with anelectromagnetic stirrer, and the mixture was heated and stirred at 90°Cfor 3 hours under a hydrogen atmosphere to activate the catalyst. Thecatalyst was separated and was used for the hydrogenolysis of isopreneperoxide polymer.

The operation was repeated 100 times using the same catalyst, and nodecrease in activity of the catalyst was found.

EXAMPLES 12-19

In the autoclave of Example 11, butadiene peroxide polymers werehydrogenated under the reaction conditions shown in Table 2. After eachhydrogenolysis reaction, the poisoned Raney nickel catalyst wasreactivated under the conditions shown in Table 2. This cycle wasrepeated for the number of times shown in the table for each Example.The results are shown in Table 2.

                                      Table 2                                     __________________________________________________________________________              Reaction Conditions                                                                    Reac-                                                                         tion     Repeated                                                                            Reactivation Conditions                         butadiene  Raney                                                                             tempe-                                                                            Reaction                                                                           use of           Tempe-                           Exam-                                                                             polymer                                                                             peroxide                                                                           nickel                                                                            rature                                                                            pressure                                                                           catalyst         rature                           ple (g)   (mole)                                                                             (g) ( °C)                                                                      (kg/cm.sup.2)                                                                      (time)                                                                              Alkali     (°C)                      __________________________________________________________________________    12   20    0.23 10  90  10   1                                                     20    0.23 10  90  10   45   0.3N-LiOH aq. sol.                                                                        130                                                                 100 cc                                    13   20    0.23 10  50  300  1                                                     20    0.23 10  50  300  70   4N-KOH aq. Sol.                                                                           70                                                                  100 cc                                    14   20    0.23 10  70  50   1                                                     20    0.23 10  70  50   90   0.5N-KOH ethanol                                                                          90                                                                sol. 100 cc                                 15*  20    0.23 10* 70  50   1                                                     20    0.23 10* 70  50   80   0.5N-Ba(OH).sub.2                                                                         100                                                               aq. sol 100 cc                                   20    0.23 10  70  100  1                                                16*  20    0.23 10  70  100  20   0.1N-NaOH aq. sol.                                                                        70                                                                  100 cc                                         20    0.23 10  70  100  70   0.5N-NaOH aq. sol.                                                                        90                                                                  100 cc                                    17   20    0.23 10  90  50   1                                                     20    0.23 10  80  50   50   3N-ammonia 100 cc                                                                         100                             18   20    0.23 10  70  50   1                                                     20    0.23 10  70  50   60   0.5N-CH.sub.3 COONa                                                                       90                                                                aq. sol. 100 cc                             19   20    0.23 10  70  50   1                                                     20    0.23 10  70  50   60   0.5N-K.sub.2 CO.sub.3 aq.                                                                 90l.                                                                100 cc                                    __________________________________________________________________________    Product                                                                           1,4-  1,2-      Yield of 1,4-                                             Exam-                                                                             butanediol                                                                          butanediol                                                                              butanediol                                                ple (g)   (g)   other                                                                             (%)                                                       __________________________________________________________________________    12  11.59 3.80  1.95                                                                              56                                                            11.39 3.75  1.97                                                                              55                                                        13  11.58 3.86  1.91                                                                              56                                                            10.97 3.65  2.03                                                                              53                                                        14  11.59 3.82  1.93                                                                              56                                                            11.40 3.67  1.94                                                                              55                                                        15* 11.60 3.83  1.92                                                                              56                                                            11.17 3.74  2.00                                                                              54                                                            11.61 3.87  1.91                                                                              56                                                        16* 10.93 3.60  2.04                                                                              53                                                            11.41 3.80  1.98                                                                              55                                                        17  11.58 3.83  1.96                                                                              56                                                            11.41 3.79  2.01                                                                              55                                                        18  11.60 3.82  1.97                                                                              56                                                            11.40 3.77  2.00                                                                              55                                                        19  11.58 3.75  1.98                                                                              56                                                            11.41 3.80  1.92                                                                              55                                                        __________________________________________________________________________     *In Example 15, a modified Raney nickel catalyst containing 1% chromium       was used.                                                                     *In Example 16, the poisoned Raney nickel was treated at 70°C with     0.1N-NaOH each time after the reaction for 20 times, and thereafter was       treated at 90°C with 0.5N-NaOH thereafter.                        

Having now fully described this invention, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit or scope of the inventionas set forth herein.

What is claimed as new and intended to be covered by Letters Patent is:
 1. A method for the hydrogenolysis of an organic peroxide polymer which comprises mixing a solution of the organic peroxide polymer with Raney nickel; hydrogenating the organic peroxide polymer with hydrogen to form a diol product; separating the poisoned Raney nickel; reactivating the poisoned Raney nickel by contacting with a 0.1-5 N aqueous or lower alcohol solution of an activating reagent selected from the group consisting of ammonia, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates and alkali metal carboxylates containing from 1 to 4 carbon atoms, and alkaline earth metal carboxylates containing from 1 to 4 carbon atoms at 20°-200°C under an inert gas atmosphere from 2 to 8 hours, and recycling the reactivated Raney nickel by mixing with a solution of the organic peroxide polymer.
 2. The method of claim 1, wherein said activating reagent is an alkali metal carbonate.
 3. The method of claim 1, wherein said activating reagent is an alkali metal carboxylate having from 1 to 4 carbon atoms.
 4. The method of claim 1, wherein said activating reagent is an alkaline earth metal hydroxide.
 5. The method of claim 1, wherein said activating reagent is an alkaline earth metal carbonate.
 6. The method of claim 1, wherein said activating reagent is an alkaline earth metal carboxylate having from 1 to 4 carbon atoms. 